CN102484207B - Organic el element, process for manufacturing organic el element, and organic el display device - Google Patents
Organic el element, process for manufacturing organic el element, and organic el display device Download PDFInfo
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- CN102484207B CN102484207B CN201080029373.1A CN201080029373A CN102484207B CN 102484207 B CN102484207 B CN 102484207B CN 201080029373 A CN201080029373 A CN 201080029373A CN 102484207 B CN102484207 B CN 102484207B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
Abstract
An organic EL element, comprising a substrate (20), a lower electrode layer (21), an upper electrode layer (26), and an organic layer (22). The organic layer (22) is placed between the pair of electrode layers (21, 26). The electrode layers (21, 26) and the organic layer (22) are laminated upon the substrate (20). The hole-injecting layer (23) and/or the luminescent layer (24) of the organic layer (22) are formed by an electro-spray process, and have a film-like structure in which fine particles are linked together continuously.
Description
Technical field
The present invention relates to organic EL (electroluminescence) element etc., particularly relate to the structure of the organic layer containing organic EL element.
Background technology
In recent years, carry out the exploitation of organic EL element energetically always.Use the display of organic EL element not need backlight and Polarizer, dynamic range and visual angle excellence, be conducive to slimming and cost degradation, the backbone therefore as display of future generation enjoys expectation.
In organic EL element, generally possess between the anode and negative electrode of film-form and carry out self luminous organic EL layer by applying voltage, at organic EL layer, lamination has hole injection layer, transfer layer, luminescent layer, hole blocking layer, electron supplying layer etc.
Each layer of these organic EL passes through the situation more (vacuum vapour deposition) of vacuum evaporation film forming, and a part is sometimes also by utilizing the coating of spin-coating method to carry out film forming (rubbing method).
In addition, also propose there is the film build method (patent documentation 1 ~ 3) using electrojet.In electrojet method, such as, directly charged to the solution of coating material, the microparticle of solution is repelled each other, this solution is scattered from nozzle.And, between this nozzle and the substrate as target, form electric field, make this electric field action in charged drop and the drop making this charged drops to substrate.By adjusting the conditions such as the intensity of electric field, solvent, distance between nozzle and substrate, the state of coating material when landing can be controlled.
But, in patent documentation 1 and patent documentation 2, and the not mentioned condition for being suitable for organic EL element.On the other hand, in patent documentation 3, by coating material from nozzle to substrate electrostatic spray, by being arranged at the mask of the insulator between nozzle and substrate, carry out film forming at the substrate of conductivity selectively.Voltage is applied to mask, makes to be not attached to mask by the microparticle of the coating material of spraying, be attracted to substrate.
But in order to make OLED display show with colour, general use is set up in parallel 3 sub-pixels comprising redness (R), green (G), blue (B) in one pixel, and controls the method for the luminescence of these each sub-pixels.For this reason, the luminescent layer (patterning) selectively these each sub-pixels being formed to the shades of colour sent is needed.
As such patterning techniques, except patent documentation 3, also propose there is various motion (patent documentation 4 ~ 7).
In patent documentation 4, disclose the method using metal mask by vacuum evaporation patterning.
In patent documentation 5, disclose and use ink jet recording head that the method for transfer layer patterning is injected in the hole of organic EL element.
In patent documentation 6, disclose when be coated with mask is set between liquid chamber and substrate, to substrate spraying coating fluid time, voltage applied to mask and control the direct of travel of coating fluid, carrying out the method be coated with selectively.
In patent documentation 7, disclose when arranging mask between test portion boat and substrate, when making the formation material of organic EL layer carry out evaporation, apply voltage to mask and control the direct of travel that it forms material, evaporation forms the method for material selectively.
Prior art document
Patent documentation
Patent documentation 1: United States Patent (USP) No. 6350609 specification
Patent document 2: United States Patent (USP) No. 6787313 specification
Patent document 3: Japanese Unexamined Patent Publication 2007-229851 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-075638 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2000-106278 publication
Patent document 6: Japanese Unexamined Patent Publication 2001-345176 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2001-345177 publication
Summary of the invention
Invent problem to be solved
But above-mentioned vacuum vapour deposition and rubbing method, also have, in the method for patent documentation 3 ~ patent documentation 7 that the technology of patterning is correlated with, there is following problem respectively.
(problem of vacuum vapour deposition)
When forming multiple layers by vacuum vapour deposition lamination, the situation that the evaporation rate of each layer is different is more.Therefore, circulation timei of manufacturing process limit by the slowest layer of evaporation rate, realizing high productivity forms bottleneck.
In addition, in vacuum vapour deposition, usually adopt during evaporation and use crucible to carry out the electrical resistance heating heated.But the Temperature Distribution of the inside of crucible easily becomes uneven, be therefore difficult to maintain certain evaporation rate and critically control evaporation.
In addition, in order to form uniform film, need to make the distance between vapor deposition source and substrate become large, compared with the size of substrate, vacuum deposition apparatus becomes large in rain.Its result, cause a large amount of part of material evaporation beyond substrate, material use efficiency is obviously impaired, and equipment cost uprises.
(problem of rubbing method)
Rubbing method is widely used in display industry, such as, establish and have the glass substrate high accuracy of G8 and G10 size and carry out the technology of film forming equably.But for organic EL element, need the multiple layer of lamination, only otherwise carry out the thawless process such as firing to the film formed, the film of previous lamination, by dissolution with solvents contained in the film of new lamination, can not form suitable laminated construction.
For the material of high score subclass, the liquid repellency can distinguishing solution repeats coating.But be difficult to the film that suitably lamination is all, therefore, actual conditions use the organic EL element characteristic of such material poor, do not have the features of practical application in life-span and efficiency.
On the other hand, for the material of low molecule class, itself be difficult to carry out film forming by rubbing method.Be difficult to the raising taking into account dissolubility and characteristic, the material that can utilize also is restricted.
(problem of mask evaporation process)
In the mask evaporation process that patent documentation 4 is such, owing to also carrying out evaporation to mask, therefore partly can only utilize material.Such as, when carrying out evaporation to 3 sub-pixels (RGB) respectively in order to colorize, the material of 2/3 is dropped, if the utilization ratio of the material of vacuum vapour deposition is about 10%, then the utilization ratio of the material in mask evaporation process is only a few percent.
In addition, because the distance between vapor deposition source and substrate is comparatively large, therefore produce the shade of mask according to the position of vapor deposition source, cause film forming bad.In addition, if display maximizes, then also the need area that make mask corresponding to it becomes greatly, and during manufacture for giant display, existence limits.
(problem of ink-jet method)
Because ink-jet method that patent documentation 5 the is such solution that can drip in desired position carries out film forming, therefore having can the advantage of patterning as required.But owing to there is position deviation or the blocking etc. of shower nozzle of machinery in ink-jet method, the precision of position that therefore solution drips not is so high.In addition, also there is solution to disperse towards periphery and the worry producing the colour mixture of RGB.
Generally speaking, in order to form uniform film by ink-jet method, form to load the solution needs dripped the encirclement being called as dike.In addition, must carry out surface treatment and improve the hydrophily of part forming film fully, preparatory process easily becomes complicated.There is the worry that the characteristic owing to carrying out surface treatment and film reduces.In addition, because the film containing the material being dissolved in homogeneous solvent each other can not direct lamination, therefore, it is possible to the material used is restricted.Therefore, ink-jet method is current and be not suitable for the most excellent material of characteristic and laminated construction.
(problem of the method for patent documentation 3 grade)
On the other hand, the method for patent documentation 3 and patent documentation 6,7, by applying voltage to mask, can reduce the adhesion amount of coating material to mask, can improve the utilization ratio of material.
But, according to the display manufactured, need to make mask respectively, there is the problem of on-demand shortcoming.
The object of the present invention is to provide the organic EL element of the utilization ratio excellence of on-demand, material.
For the method for dealing with problems
The present invention is a kind of organic EL element, possesses: substrate; Comprise the pair of electrode layers of lower electrode and upper electrode; And organic layer, above-mentioned organic layer is arranged between above-mentioned pair of electrode layers, above-mentioned pair of electrode layers and above-mentioned organic laminate are on aforesaid substrate, above-mentioned organic layer has more than one layer, this more than one layer comprises the luminescent layer by applying voltage luminescence, and at least one layer that above-mentioned organic layer has has microparticle and combine continuously and the membrane structure that formed.
Above-mentioned luminescent layer can have above-mentioned membrane structure.
In addition, above-mentioned organic layer also can comprise the second layer as at least any one the performance function in electric charge injection layer and charge transport layer, and the above-mentioned second layer has above-mentioned membrane structure.
Above-mentioned membrane structure can comprise low molecule organic material.
Above-mentioned membrane structure preferably uses electrojet method to be formed.
In addition, in organic EL element, can: above-mentioned lower electrode is formed multiple on aforesaid substrate, above-mentioned multiple lower electrode is formed the above-mentioned luminescent layer with above-mentioned membrane structure respectively, and above-mentioned multiple luminescent layer comprises the multiple luminescent layers using the color of the luminescence of electrojet method formation different.
In addition, in organic EL element, can: above-mentioned lower electrode is formed multiple on aforesaid substrate, above-mentioned multiple lower electrode is formed the above-mentioned second layer with above-mentioned membrane structure respectively, above-mentioned multiple second layer comprises the multiple second layers using the thickness of electrojet method formation different, also can material difference.
Such organic EL element can use following manufacture method manufacture, and above-mentioned manufacture method comprises: the lower electrode formation process forming above-mentioned lower electrode on aforesaid substrate; With the film formation process utilizing electrojet method, between injection nozzle and the substrate being formed with above-mentioned lower electrode, form electric field, in this condition, scatter the solution of charged coating material from above-mentioned injection nozzle to aforesaid substrate, in above-mentioned film formation process, control the current potential of above-mentioned lower electrode.
In addition, when being formed with multiple above-mentioned lower electrode on aforesaid substrate, following manufacture method can be used to manufacture organic EL element, and above-mentioned manufacture method comprises: the lower electrode formation process forming above-mentioned multiple lower electrode on aforesaid substrate; With the film formation process utilizing electrojet method, between injection nozzle and the substrate being formed with above-mentioned multiple lower electrode, form electric field, in this condition, scatter the solution of charged coating material from above-mentioned injection nozzle to aforesaid substrate; Above-mentioned film formation process comprises the control of Electric potentials operation of the current potential controlling above-mentioned lower electrode, in above-mentioned control of Electric potentials operation, the process of giving the electric charge of the same race with the solution of above-mentioned coating material is carried out at least any one lower electrode in above-mentioned multiple lower electrode.
Such organic EL element is applicable to organic EL display.
Invention effect
According to the present invention, productivity can be provided excellent and the organic EL element etc. of material cost can be suppressed.
Accompanying drawing explanation
Fig. 1 is concept map when using the electrojet method that the present invention relates to carry out film forming.
Fig. 2 is the luminous picture of PL on the conjunctival surface of microparticle.A () is the microparticle binding film that film forming obtains under unsuitable condition, (b) is the microparticle binding film that obtains of film forming under suitable condition.
Fig. 3 is the AFM picture of the film in Fig. 2 (b).
Fig. 4 is the sectional view for illustration of the conjunctival structure of microparticle.
Fig. 5 is concept map when using the electrojet method that the present invention relates to carry out patterning.
Fig. 6 is by luminous for the PL of the film of luminescent pigment patterning picture.
Fig. 7 be the major part of organic EL display in the first execution mode overlook ideograph.
Fig. 8 is the X-X line sectional view in Fig. 7.
Fig. 9 is the cross-sectional modes figure of the laminated construction representing organic EL element.
Figure 10 is the skeleton diagram of electrical spraying device.
Figure 11 is the sequential chart of the control of Electric potentials of each sub-pixel.
Figure 12 is the figure of comparing element characteristic.
Figure 13 is the figure of comparing element characteristic.
Figure 14 is the variation of the sequential chart of the control of Electric potentials of each sub-pixel.A (), (b) represent the sequential chart of different control of Electric potentials respectively.
Figure 15 be light-emitting component in the second execution mode overlook ideograph.
Figure 16 be the laminated construction of the light-emitting component represented in the second execution mode overlook ideograph.
Figure 17 is the figure of the chemical formula representing main material.
Embodiment
Below, based on accompanying drawing, embodiments of the present invention are described in detail.Wherein, the following description is only illustrate in essence, does not limit the present invention, its applicable thing or its purposes.
(membrane structure that microparticle combines continuously and formed)
In the organic layer of the organic EL element that the present invention relates to, exist and there is microparticle combine continuously and the layer (also referred to as microparticle binding film) of membrane structure that formed.The microparticle binding film of present embodiment uses electrojet method to be formed, and is therefore first described electrojet method.
Fig. 1 represents the concept map of the film build method using electrojet method.In figure, 1 by film forming object, and 2 is solution side electrodes, and 3 is injection nozzles, and 4 is high voltage sourcies, and 5 is the solution (also referred to as masking liquid) of coating material.
In electrojet method, in the anode and negative electrode of high voltage source 4, one side is connected with by film forming object 1, and the opposing party is connected with the solution side electrode 2 that impregnated in masking liquid 5.And, give contrary electric charge respectively to masking liquid 5 with by film forming object 1, injection nozzle 3 and by film forming object 1 between be formed with electric field.In this condition, charged masking liquid 5 is scattered by injection nozzle 3.The drop scattered, by electric field leading, drops to by film forming object 1 and carries out film forming.
Now, drop miniaturization by the electrostatic force of self of distribution, compares with the injection of ink-jetting style with the spraying of common injection, becomes especially little, therefore, it is possible to form the film of the densification of N/D.
Such as, Fig. 2 represents the luminescent layer of supposition organic EL element, by PL (luminescence generated by light) the luminous picture of electrojet method when having been carried out the film forming of luminescent pigment by film forming object.(a) of this figure is the film that the drop when landing obtains in film forming under larger granular unsuitable condition, and (b) of this figure is the film that obtains of film forming under suitable condition.In addition, PL luminescence is by irradiating excitation source, the phenomenon of luminescent pigment stimulated luminescence.
As shown in this figure (a), the drop when landing becomes large, produces non-luminous position (stain) throughout.In addition, in such film, easily cause the electric leakage between electrode, the flowing of electric charge also becomes unstable.
On the other hand, as shown in this figure (b), if film forming under suitable condition, then can obtain uniform luminescence.This represents that the very fine microparticle of drop connects and seamlessly film forming continuously.
Such as, Fig. 3 represent the AFM (atomic force microscope) of the film in (b) of Fig. 2 as.When watch these as time, although less, at fine concavo-convex to droplet particles of the surface observation of film.Like this, the film suitably formed by electrojet method, even if observe at micron or Nano grade, also pile up and gapless continuous print membrane structure equably in fine droplet particles, its surface is formed with the fine concaveconvex shape of droplet particles.That is, the film formed by electrojet method has the character of film and particle concurrently.
Can think that such film is formed as shown in Figure 4.That is, can think, when drop drops to by film forming object, also remain solvent, the drop of adjacent landing simultaneously connects each other by its surface part and drying rapidly, and result forms continuous print film with the state remaining granular shape.In addition, in the figure, 7 represent this film, the granular part (granular core) of 8 expression films 7, the joint portion of the film 7 that 9 these granular core of expression are joined integrally.
In the present invention, be " membrane structure that microparticle combines continuously and formed " by such organization definition.
(microparticle binding film is to the utilization of organic EL element)
The conjunctival granular core of microparticle is very little Nano grade.The density of granular core is relatively large, expects that electrical characteristics and the characteristics of luminescence uprise.For microparticle binding film, entirety on film surface forms the fine concavo-convex of Nano grade, and therefore, its surface area becomes in fact large, and rate of drying accelerates.That is, without the need to carrying out special dry process, manufacturing process can be made to simplify.
In addition, in ink-jet method, the high boiling solvent of the many uses of the homogenizing in order to film, but in this case, in order to make solvent seasoning, need vacuum heating treatment etc., manufacturing process easily becomes complicated.
In addition, for microparticle binding film, easily the laminating of film can be carried out.As mentioned above, be difficult to form laminated construction by general rubbing method.But adopt electrojet method, the drop of distribution is almost simultaneously dry in landing, therefore, it is possible to the film ground of insoluble solution lower floor carries out lamination.
In addition, the surface area at the film contacted with each other and the interface of film becomes greatly, injects effect therefore, it is possible to improve.
Can not using macromolecular compound and use on this aspect of low molecular compound in the organic material forming film, is favourable.The organic material (low molecule organic material) of low molecule system is usually by vacuum vapour deposition film forming.In vacuum vapour deposition, by making low molecule organic material distil and fine molecule or the cluster rank of turning to, carry out evaporation film-forming.To this, the masking liquid containing low molecule organic material also can be micronized into the drop into almost cluster rank by electrojet method, scatters film forming, therefore, it is possible to form the film with vacuum evaporation equal quality.
Therefore, adopt electrojet method, can carry out laminating, also can make made by vacuum vapour deposition with current organic EL element same material, same structure organic EL element.
In addition, the size of each granular core, preferable particle size is below 100nm.When particle diameter is more than 100nm, there is the worry producing stain.In addition, particle diameter mentioned here such as can use the particle diameter measured from the AFM picture of film, and particle diameter is that below 100nm refers to and statistically do not comprise the granular core (α=0.05) of particle diameter more than 100nm.
The organic layer using electrojet method to be formed can be luminescent layer, also can be electric charge injection layer or charge transport layer.
Electrojet method is carried out under the state being formed with electric field.Therefore, because the film formed is subject to the effect of electric field, forms electric stable structure, obtain the organic EL element that reliability is high.If such as use and there is electric dipole moment or electropolarized organic material, then the film formed has electric sequence.
Therefore, if charge transport layer then can expect the improvement effect etc. of electrical characteristics, if luminescent layer then can expect the raising etc. of luminous efficiency.
(application to patterning)
Electrojet method can utilize suitably in patterning.Such as, Fig. 5 represents concept map when using electrojet method to carry out patterning.In addition, in figure, 10 is substrates, and 11a ~ 11c is the lower electrode be formed at respectively on substrate.12 is solution side electrodes, and 13 is injection nozzles, and 14 is high voltage sourcies, and 15 is masking liquids.In this example, solution side electrode 12 and lower electrode 11a, 11c are electrically connected with the positive pole of high voltage source 14 respectively, and lower electrode 11b is connected with the negative pole of ground connection.
In electrojet method, owing to being formed with electric field being formed with between the substrate 10 of lower electrode 11a ~ 11c and injection nozzle 13, therefore, in this condition, when scattering charged masking liquid 15 from injection nozzle 13 to substrate 10 side, charged drop is subject to the effect of electric field, is directed to power line and conjugates.Therefore, if control the current potential of lower electrode 11a ~ 11c, then can only in arbitrary lower electrode film forming.
Such as, in the figure, because lower electrode 11a, 11c are endowed the positive charge of the same race with drop, drop produces electricity to be repelled and not to drop to lower electrode 11a, 11c.On the other hand, lower electrode 11b is endowed negative electrical charge, and drop drops to lower electrode 11b selectively.
Like this, by the current potential of difference control electrode, required electrode can be selected to carry out film forming from multiple electrode.
Like this operation is illustrated and by luminous for the PL of the film of luminescent pigment patterning picture in Fig. 6.In figure, 18 is the regions of not carrying out film forming, and 19 is the light-emitting zones after film forming.There is lower electrode 11b in the downside of light-emitting zone 19, do not carrying out region 18 lower electrode 11a or 11c of film forming.Like this, can reliably patterning.
In order to organic EL element is utilized in the display (organic EL display) that can carry out colored display, the organic EL element of a formation pixel is needed to be divided into multiple sub-pixel, be divided into the sub-pixel of more than 3 in reality, each sub-pixel use R (red), G (green), B (indigo plant) etc. the different luminescent material of the color of luminescence by luminescent layer patterning.
Therefore, when forming luminescent layer at each sub-pixel, controlling the current potential of each lower electrode as described above, arbitrary luminescent layer can be formed on arbitrary lower electrode.Like this, do not need to prepare special mask, freely can carry out film forming according to the surface configuration of lower electrode, therefore manufacturing process is simplified, and on-demand is also good.
(raising of colorrendering quality)
Owing to being organic substance for the luminescent material of organic EL element, self have wide emission spectrum, colour purity is not very high.In the display, what such as require NTSC than the colorrendering quality being more than 100% is more, and in the luminescent spectrum of main luminescent material, NTSC exists boundary than the colorrendering quality being about 70%.
But the thickness forming each layer of organic layer is about 10 ~ 60nm.The suitableeest thickness in the organic layer of shades of colour is different, but is generally about 100 ~ 150nm as the thickness of organic layer entirety.The thickness of this degree is just easily subject to the interference effect with visible light, and therefore the colorrendering quality of this organic layer changes significantly due to the change a little of thickness.In other words, colour purity can be improved by the thickness adjusting organic layer.
That is, adopt electrojet method, patterning can be carried out to the organic layer of each shades of colour, therefore, it is possible to change thickness simply to each organic layer.Such as, desired thickness can be formed to each assorted organic layer controlling potential successively, in a series of film forming procedure, adjust film formation time by the current potential of control electrode, side by side can form different each organic layer of thickness.
Therefore, by controlling the thickness of the material of the layer, such as electric charge injection layer and the charge transport layer etc. that form beyond the luminescent layer of organic layer, the colour purity of shades of colour can be improved, improving the colorrendering quality of display.
(realization of high efficiency, long lifetime)
The usual band gap of different luminescent materials of luminous color is different with molecular structure, and the suitableeest material of therefore corresponding from it charge transport layer etc. is also often different.But, in existing method, be difficult to change material to often kind of luminescent material and by charge transport pattern layers, be generally whole and form charge transport layer with identical material.
To this, adopt electrojet method, can high cycle and carry out patterning at low cost, therefore, it is possible to use the suitableeest material in the luminescent material of each luminescent layer to form charge transport layer.Each sub-pixel can be made effectively to play its function, the high efficiency of organic EL element and display, long lifetime can be realized.
< first execution mode >
Then, be described in detail with reference to concrete execution mode.
(structure of organic EL element)
Fig. 7 ~ Fig. 9 represents the organic EL element of the display part of the color monitor (organic EL display) forming present embodiment.Fig. 7 is the figure of the basic structure of watching organic EL element from it.Fig. 8 is X-X line sectional view in Fig. 7.Fig. 9 is the laminated construction of organic EL element.In these figures, 20 is glass substrates, 21 (21a ~ 21c) are lower electrode (anodes), 22 is organic layers, 23a hole injection layer, and 23b is hole transporting layer, 24 (24a ~ 24c) are luminescent layers, 25 is electron supplying layers, and 26 is upper electrode (negative electrodes), and 27 is distance pieces.Fig. 7 represents 2 pixel portion, and 1 pixel is split into 3 sub-pixels 28 of B sub-pixel 28a, G sub-pixel 28b, R sub-pixel 28c.
On glass substrate 20, the anode 21 of multiple band shape, 21 ... be formed as striated.Each anode 21 is arranged side by side across the spacing of regulation.These anodes 21 are formed by the AL/ITO with the transparency.Specifically, each anode 21 is formed with the width of 120 μm respectively, and the width in gap is 20 μm.Anode 21 forms (lower electrode formation process) by the patterning of sputtering method, photoetching process.
With the mode orthogonal with anode 21 be formed multiple wire distance piece 27,27 ...These distance pieces 27 separate predetermined distance and side by side.Specifically, the Breadth Maximum of each distance piece 27 is 15 μm, and the width at interval is 340 μm.Each distance piece 27 uses photosensitive polyimide resin by photoetching process patterning, and the glass substrate 20 being formed with anode 21 erects as wall-like.The width of distance piece 27 becomes gradually from base end side (substrate 20 side) towards front large (reverse tapered shape).In addition, the material of distance piece 27 is not restricted to polyimide resin, can suitably select as required.Such as, also can be inorganic matter.
Anode 21 is formed hole injection layer 23a and hole transporting layer 23b (second layer).In hole transporting layer 23b, the general material of organic EL element or organic photoconductor can be used.As its concrete example, such as, inorganic p-type semiconductors material, porphyrin compound, N can be enumerated, N '-bis--(3-aminomethyl phenyl)-N, N '-bis--(phenyl)-benzidine (TPD), N, the aromatic uncle amine compound, hydrazone compound, quinacridone compound, styrylamine compound etc. of N '-bis-(naphthalene-1-base)-N, N '-diphenyl-benzidine (NPD) etc.Detailed content is described below, and the thickness of hole injection layer 23a is different in each each sub-pixel 28, is formed by patterning.
On each hole transporting layer 23b etc., patterning has the luminescent layer 24 sending the light of different colours by applying voltage respectively.Specifically, first anode 21a is formed the luminescent layer 24a of the light of the look (B) that turns blue, second plate 21b is formed the luminescent layer 24b of the light of green-emitting (G), the 3rd anode 21c is formed the luminescent layer 24c of the light of rubescent look (R).The thickness of each luminescent layer 24 any one be 30nm.
On each luminescent layer 24, be formed with the electron supplying layer 25 of the thickness of 20nm.And, electron supplying layer 25 is formed negative electrode 26.The structure of negative electrode 26 is LiF (1nm)/MgAg (5nm)/Al (3nm).In addition, the negative electrode 26 of present embodiment, hole transporting layer 23b, electron supplying layer 25 are to cover the mode of whole of pixel by vacuum vapour deposition film forming.
Split by the distance piece 27 of vertebral body shape in negative electrode 26 grade of whole film forming.Specifically, the negative electrode 26 etc. of the striated of the width of 330 μm is formed.Like this, each sub-pixel 28 of 120 μm × 330 μm is formed by mutually orthogonal anode 21 and negative electrode 26.And, form 1 pixel by 3 sub-pixel 28a ~ 28c of adjacent RGB.
In addition, in this color monitor, in anode 21, use reflexive electrode, use the electrode of semi-transparency at negative electrode 26, become the top emission structure of taking out the light sent from the opposition side of glass substrate 20.By there is the interference effect of light between semipermeable electrode and reflexive electrode, can obtain improving effect (microcavity effect) by the colourity caused that is increased sharply of emission wavelength.
(patterning of hole injection layer)
The hole injection layer 23a of present embodiment, uses electrojet method to form (film formation process).First, in the mixed solvent of oxolane (THF) and dimethylbenzene, dissolving the material (also referred to as hole injection layer material) for forming hole injection layer, making masking liquid.In addition, the material of low molecule system is used in hole injection layer material.In addition, low molecular material mentioned here refers to the metal complex fluorescent material of unit point sub-connection or the oligomer of phosphorescent compound, fluorescent chemicals etc. with epipolic molecule and 1 ~ 8.
Specifically, three (oxine) aluminium (III) (Alq), 4 such as can be enumerated as metal complex fluorescent material, 4 '-bis-(N-(9,9-bis-(6) fluorene methyl-2-base)-N-phenylamino) biphenyl (DFLDPBi), two (2-methyl-oxine) (4-phenylphenol) aluminium (III) (BAlq).
(acetylacetone,2,4-pentanedione) two (2 such as can be enumerated as phosphorescent compound, 3, 5-triphenylpyridinium) iridium (III) (Ir (tppr) 2 (acac)), two (2-(4 ', 6 '-difluorophenyl) pyridine-N, C2 ') pyridinecarboxylic conjunction iridium (III) (FIrpic), three (2-phenylpyridine-N, C2 ') iridium (III) (Ir (ppy) 3), acetopyruvic acid two (2-phenylpyridine-N, C2 ') iridium (III) (Ir (ppy) 2 (acac)), acetopyruvic acid two (2-phenylbenzothiazol base-N, C2 ') iridium (III) (Ir (bt) 2 (acac)), three (2-phenylchinoline-N, C2 ') iridium (III) (Ir (pq) 3), acetopyruvic acid two (2-phenylchinoline-N, C2 ') iridium (III) (Ir (pq) 2 (acac)), acetopyruvic acid two (2-(2 '-benzo (4, 5-α) thienyl) pyridine-N, C3 ') iridium (III) (Ir (btp) 2 (acac)), acetopyruvic acid two (1-phenyl isoquinolin quinoline-N, C2 ') iridium (III) (Ir (piq) 2 (acac)), (acetylacetone,2,4-pentanedione) two (2, two (4-fluorophenyl) quinoxaline of 3-) iridium (III) (Ir (Fdpq) 2 (acac)), 2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-porphyrin platinum (II) (PtOEP).
As fluorescent chemicals, such as can Lie Ju perylene, 2,5,8,11-tetra-(tert-butyl group) perylene (TBP), 4,4 '-bis-(2-(N-ethyl carbazole-3-base) vinyl) biphenyl (BCzVBi), 5,12-diphenyl aphthacene, N, N '-dimethylquinacridone (DMQd), N, N '-diphenylquinacridone (DPQd), 4-dicyano methylene-2-isopropyl-6-[2-(1,1,7,7-tetramethyl julolidine-9-base) vinyl]-4H-pyrans (DCJTI), rubrene, coumarin 6, cumarin 30.
Figure 10 represents used electrical spraying device 30.As shown in the drawing, electrical spraying device 30 possess there is capillary 31a dissemination apparatus 31, for support fixing base 20 platform 32, for giving the first high voltage source 33 of electric charge, masking liquid lateral electrode 34 and voltage-operated device 35 etc. to masking liquid.Voltage-operated device 35 is equipped with for giving the second high tension voltage 35a of electric charge and the control system etc. for controlling its voltage to each electrode 21 of substrate 20.Each high voltage source 33,35a have the ability that can form every 1cm 1KV electric field.Capillary 31a uses the glass tube that stretching internal diameter is about 1mm to process the universal product obtained.By charged, the drop miniaturization of distribution, therefore do not need as ink-jet method there is fine outlet.Therefore, electrojet method has the advantage that masking liquid is difficult to block.
Platform 32 vertically can slide with level side and control, and film forming is evenly carried out.At the upper surface of platform 32, the substrate 20 being formed with anode 21 is set.After platform 32 arranges substrate 20, the portion of terminal being arranged at one end of each electrode 21 is electrically connected with voltage-operated device 35.Operating voltage control device 35 and set various condition, can select desired electrode 21 to apply voltage thus, at random can also set application time and the opportunity of this voltage.
In the present embodiment, the distance between the substrate 20 on the front end of capillary 31a and platform 32 is set as 5cm.In first high voltage source 33, its side of the positive electrode is connected with masking liquid lateral electrode 34, its negative side ground connection is applied the voltage of 5KV.That is, masking liquid is applied to the voltage of+5KV, give positive charge.
On the other hand, each electrode 21 of substrate 20 side is alternately controlled to be the electronegative connection that the positively charged be connected with the side of the positive electrode of the second high voltage source 35a connects and is connected with the negative side of the second high voltage source 35a by voltage-operated device 35.The negative side ground connection of the second high voltage source 35a, by being connected with side of the positive electrode, applies the voltage of+7V to electrode 21.That is, the drop being endowed positive charge does not drop to the electrode 21 of positive charge connection, and the electrode 21 only dropping to negative electrical charge connection carries out film forming.In addition, be set to+7V in the present embodiment, but its above voltage can certainly be set as.
Also as shown in Figure 8, in order to show microcavity effect most effectively, the positive hole injecting layer 23a forming the positive hole injecting layer 23a of 30nm respectively on the first anode 21a of B sub-pixel anode 28a, the second plate 21b of G sub-pixel anode 28b is formed the positive hole injecting layer 23a of 60nm, form 120nm on the third anode 21c of R sub-pixel anode 28c.
Like this, in order to by multiple positive hole injecting layer 23a patternings different for thickness, in the present embodiment, each positive hole injecting layer 23a is defined continuously.That is, when scattering masking liquid, to switch the mode setting voltage control device 35 of the current potential of each electrode 21 in required time continuously.
Figure 11 represents the sequential chart of its control of Electric potentials.In figure, the longitudinal axis represents the voltage putting on each anode, and transverse axis represents the elapsed time.As shown in the drawing, first, negative electrical charge connects the 3rd anode 21c, and positive charge connects first anode 21a and second plate 21b, makes only to carry out film forming to R sub-pixel 28c.Then, similarly, only to connect in the mode of G sub-pixel 28b film forming, finally only to connect in the mode of B sub-pixel 28a film forming, switching controls is carried out successively.Adopt the method, the different film of thickness can be formed respectively, therefore, it is possible to precision carries out the adjustment of thickness higher.
After a series of process, the solvent of each hole injection layer 23a is almost dry, therefore not thinks and needs specially to carry out drying process.Especially, carry out the better situation of drying process although also have according to the kind of hole-injecting material, also can relax firing temperature and time in this case, therefore, it is possible to reduce the damage of heat.
The each hole injection layer 23a formed like this is formed with hole transporting layer 23b.Its film build method can use electrojet method, also can use vacuum vapour deposition.Adopt electrojet method, can not have an impact to the hole injection layer 23a of lower floor and lamination simply.In addition, in the present embodiment, by utilizing vacuum vapour deposition to carry out film forming to whole face, hole transporting layer 23b is formed with.
(patterning of luminescent layer)
Each luminescent layer 24 is also same with hole injection layer 23a, uses electrojet method and patterning (film formation process).But, different from masking liquid during hole injection layer 23a.That is, the luminescent material forming luminescent layer 24 comprises the composite material of the guest materials of material of main part and mixing often kind of color (luminescent pigment: be Ir complex compound) here.Guest materials relative to the mixing ratio of material of main part with mass ratio range for 5%.These materials are dissolved in respectively the mixed solvent of NMP and THF, make masking liquid.
In addition, when film forming, each sub-pixel 28 uses the masking liquid of different materials, therefore prepares dissemination apparatus 31 to each masking liquid, controls in the mode that the opportunity of the switching of the masking liquid of voltage-controlled opportunity and distribution is synchronous.After these a series of process, the solvent of each luminescent layer 24 is also almost dry, not thinks and needs specially to carry out drying process.
The each luminescent layer 24 formed like this is formed with electron supplying layer 25.Its film build method can use electrojet method, also can use vacuum vapour deposition.Then, this electron supplying layer 25 forms negative electrode 26 by vacuum evaporation, completes the laminated construction of organic EL element.
(the microparticle binding film of present embodiment)
In order to the structure of each film to the microparticle binding film formed by present embodiment (hole injection layer 23a and luminescent layer 24) carries out detailed research, carry out the observation of AFM picture.Its result, confirms that any one film is formed by the nanometer microparticle of about 1 ~ 5nm.In addition, in these microparticles, the combination integral with one another of adjacent microparticle, seamlessly connects continuously along film surface.Nanometer microparticle also connects continuously on the thickness direction of film, and microparticle binding film forms fine and close structure.
(display characteristics of present embodiment)
About the display of present embodiment, evaluation is compared to colour purity and element characteristic.
(colour purity)
The colour purity of existing display is R (0.67,0.33), G (0.30,0.63), B (0.15,0.18), NTSC ratio during white displays is 62%, relative to this, the colour purity of the display of present embodiment is R (0.68,0.33), G (0.18,0.74), B (0.13,0.07) the NTSC ratio, during white displays is 101%.
(element characteristic)
In addition, made the display (comparative example) of same structure by vacuum vapour deposition, compare display (embodiment) and the element characteristic (current efficiency and IV characteristic) of present embodiment.
Figure 12 and Figure 13 represents the characteristic of the current efficiency comparing B sub-pixel.
Its result, embodiment is compared with comparative example, and current efficiency improves 12%, and the magnitude of current improves 1.8 times.In other sub-pixel, current efficiency improves 12 ~ 15%, and the magnitude of current improves 1.5 times ~ 2 times.This can think that therefore the injection of electric charge is promoted, and the magnitude of current increases because the surface area of electric charge injection layer and luminescent layer in an embodiment becomes large.
In addition, about the raising of current efficiency, because current efficiency during high electric current in embodiment is also higher than comparative example, therefore can this is presumably because that the regularization in the stability of the material when promotion of the injection of electric charge and high electric field apply, film plays a role.
Then, the main variation of present embodiment is described.In addition, basic structure is identical, is therefore described in detail difference.
[variation 1]
In this variation, make the material of the electron supplying layer 25 in B sub-pixel 28a be different materials from the material of the electron supplying layer 25 of other sub-pixel 28b, 28c, this point is different from the embodiment described above.
As mentioned above, the band gap of the luminescent layer 24 of each sub-pixel 28, the level of HOMO with LUMO are distinguished different.Therefore, when electric charge (hole, the electronics) implanted layer at each sub-pixel 28 etc. uses identical material, might not be the suitableeest for each luminescent layer 24.
In addition, because lumo energy is than the luminescent material height 0.3eV of light sending other color, therefore there is the problem that electronics can not inject well, luminous voltage is relatively high in the luminescent material sending blue light.
Therefore, in this variation, same with above-mentioned execution mode, use electrojet method by electron supplying layer 25 patterning.
That is, after each luminescent layer 24 of formation, first, electron supplying layer 25 is formed at G sub-pixel 28b and R sub-pixel 28c.Then, different materials is used to form electron supplying layer 25 at B sub-pixel 28a.The display obtained so is also formed with the suitableeest electron supplying layer 25 at B sub-pixel 28a.Its result, the injection of electric charge is promoted, and can reduce luminous voltage.In addition, form electron supplying layer 25 by electrojet method, also obtain the effect that driving voltage reduces 0.2V.
In addition, not only at B sub-pixel 28a, also the suitableeest different material can also be used at the electron supplying layer 25 of R sub-pixel 28c and G sub-pixel 28b.In addition, not only at electron supplying layer 25, also different materials can be used too at hole injection layer 23a and hole transporting layer 23b.Further, the laminated construction of specific sub-pixel 28 can also be changed.
[variation 2]
In the above-described embodiment, in order to by multiple hole injection layer 23a patternings different for thickness, control as forming each hole injection layer 23a continuously, but be not limited thereto, the setting of patterning can be changed as required.
Figure 14 represents the method forming each hole injection layer 23a in the lump.That is, limit is simultaneously parallel forms each hole injection layer 23a, and limit is by the application time adjustment thickness of control voltage.
In this figure (a), carry out at a high speed the switching of the connection to each anode 21, repeat interrupted film forming and patterning.Total ascent time and the respective thickness of the negative electrical charge connection of each electrode 21 are proportional.Adopt the method, the film forming of each hole injection layer 23a can be completed in the identical moment.In this figure (b), the parallel film forming starting each hole injection layer 23a, completes the film forming of this hole injection layer 23a in each hole injection layer 23a in the moment of the thickness reaching defined simultaneously.Use any one method, all can form same hole injection layer 23a.
[variation 3]
In the above-described embodiment, as microparticle conjunctival materials'use low molecule organic material, even if but use the organic material (macromolecular compound) of macromolecular also similarly can carry out film forming.
As hole injection layer 23a or hole transporting layer 23b (in the organic material of high score subclass, the situation having the injection in hole and two functions of conveying concurrently is more), such as, PEDOT/PSS{Poly (ethylene-dioxythiophene)/Poly (styrenesulfonate) can be enumerated; Polyethylene dioxythiophene/poly-sulfonated phenylethylene } and the ND of Nissan Chemical society serial etc.
As the material of luminescent layer 24, such as, polyfluorene analog copolymer can be enumerated.This macromolecule organic material be have alkyl chain R, R ' fluorenes ring and the copolymerization of unit Ar (Ar ') of at least more than one aromatic series aryl compound, its chemical formula is represented by chemical formula 1 below.
In chemical formula 1, R, R ' represent alkyl chain, the unit of Ar, Ar ' expression aromatic series aryl compound, I, m are the integers of more than 1, and n is the integer of more than 0 or 1.As aromatic series aryl compound, dimethyl benzene, pyridine, benzene, anthracene, spiral shell two fluorenes, carbazole unit, benzo amine, bipyridine, diazosulfide etc. can be used.
< second execution mode >
The organic EL element of present embodiment is different from the first execution mode of patterning at this point of whole film forming.The light-emitting component 50 being assembled with the organic EL element of present embodiment mainly can use as the backlight of liquid crystal or white light source (illumination).
(structure of light-emitting component)
Figure 15, Figure 16 represent the light-emitting component 50 of present embodiment.This light-emitting component 50 has bottom emission structure, sends the light of white from the light-emitting zone being arranged at substantially entire surface.Certainly also sending the light beyond white, also can be top emission structure.
In fig .15,51 is substrates, and 52 is lower electrode (anodes), and 53 is upper electrode (negative electrodes).Organic layer 54 is provided with between these anode 52 and negative electrodes 53.As shown in figure 16, organic layer 54 is formed with hole injection layer 56, hole transporting layer 57, electronic barrier layer 58, R luminescent layer 59, G luminescent layer 60, B luminescent layer 61, hole blocking layer 62, electron supplying layer 63 and electron injecting layer 64 from substrate 51 side successively lamination.
Anode 52 and negative electrode 53 configure in mutually orthogonal mode.An end of negative electrode 53 is provided with the portion of terminal that can be connected with voltage-operated device 35, the portion of terminal that can be connected with voltage-operated device 35 is also set in an end of anode 52.The Zone Full of the part of negative electrode 53 and anode about 52 overlap forms luminous component.
(manufacture method of light-emitting component 50)
Be formed with the thickness of 150nm the anode 52 formed by ITO (indium oxide-tin oxide) on rectangle PET film (51 substrate) surface of 60mm × 60mm size.Anode 52, by photoetching process patterning, makes it be of a size of 50mm × 55mm.The substrate being formed with anode 52, such as after use acetone or IPA carry out 10 minutes ultrasonic cleansings, carries out 30 minutes UV ozone and cleans.
Then, to the substrate 51 excessively cleaned, by electrojet method, the film forming of each layer (removing electron injecting layer 64) forming organic layer 54 is carried out.Adopt electrojet method, the electrode being formed as whole planar (continuous, gapless shape) for whole face also can film forming equably.The size of thickness can by scattering time controling.In addition, owing to utilizing the film build method of electrojet method same as the above-mentioned method, therefore it illustrates and omits.
In the solvent of chloroform, NMP, THF etc., dissolve the material of each layer respectively with the concentration of regulation, support the masking liquid of each layer.The material concentration of each masking liquid is 1 ~ 10% weight.
First, on anode 52, copper phthalocyanine (CuPc) is used to form the hole injection layer 56 that thickness is 30nm at first.Then, hole injection layer 56 uses 4,4 '-bis-[N-(1-naphthyl)-N-phenyl-amino] biphenyl) (α-NPD) form the hole transporting layer 57 that thickness is 20nm.Then, hole transporting layer 57 use 4,4 '-bis--[N, N '-(3-tolyl) amino]-3,3 '-dimethyl diphenyl (HMTPD) to form the electronic barrier layer 58 that thickness is 10nm.
Electronic barrier layer 58 is formed double charge transporting red light emitting layer (thickness: such as 20nm, R luminescent layer 59).R luminescent layer 59 uses mixed solution to carry out film forming as masking liquid.This mixed solution is using the α-NPD of the material as hole transporting layer 57,3 phenyl-4-(1 '-naphthyl)-5-phenyl-1 as the material of electron supplying layer 63,2,4 triazoles (TAZ) and (acetylacetone,2,4-pentanedione) as emitting red light dopant two (2-(2 '-benzo (4,5-α) thienyl) pyridine-N, C3 ') iridium (btp2Ir (acac)) dissolves with the concentration of the ratio of 0.6: 1.4: 0.15 respectively and is made.Be dissolved as mixed solution each homogenize material, then can be formed and the film by being total to the film same composition that vapour deposition method uses these 3 kinds of material filmings to obtain.
R luminescent layer 59 is formed double charge transporting green light emitting layer (thickness: such as 20nm, G luminescent layer 60).This G luminescent layer 60 also uses mixed solution to carry out film forming as masking liquid.This mixed solution the α-NPD of the material as hole transporting layer 57, the TAZ as the material of electron supplying layer 63 and the Ir (ppy) 3 as green emitting dopant is dissolved with the concentration of the ratio of 1.0: 1.0: 0.1 to be respectively made.
G luminescent layer 60 is formed double charge transporting blue light-emitting layer (thickness: such as 10nm, B luminescent layer 61).This B luminescent layer 61 also uses mixed solution to carry out film forming as masking liquid.This mixed solution is using the α-NPD of the material as hole transporting layer 57, the TAZ as the material of electron supplying layer 63 and 2-(4 '-tert-butyl-phenyl)-5-as blue-light-emitting dopant (4 "-xenyl)-1; 3,4-oxadiazole (tBU-PBD) dissolves with the concentration of the ratio of 1.5: 0.5: 0.2 respectively and is made.By these 3 luminescent layers 59,60,61, obtain the white light-emitting layer sending white light.
B luminescent layer 61 use 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) form the hole blocking layer 62 that thickness is 10nm.Hole blocking layer 62 use three (oxine) aluminium (Alq3) form the electron supplying layer 63 that thickness is 30nm.
On electron supplying layer 63, by vacuum vapour deposition, lithium fluoride (LiF) is used to form the electron injecting layer 64 that thickness is 1nm.In addition, on electron injecting layer 64, piling up aluminium to thickness by vacuum vapour deposition is such as 300nm, forms negative electrode 53.In addition, chemical formula such as Figure 17 of main material represents.
(performance of light-emitting component)
When applying the voltage of 10V to the light-emitting component 50 completed, obtain the white luminous of 7000cd/m2.
By vacuum vapour deposition, make the light-emitting component (comparative example) with light-emitting component 50 (embodiment) same structure of present embodiment, these element characteristics are compared.
Its result, confirms: compared with comparative example, and embodiment improves 10% at the luminosity of 10V, and the magnitude of current improves 15%.
Like this, even in whole face the larger organic EL element of repeatedly lamination film forming, also can manufacture simply.Adopt electrojet method, can be filmed in an atmosphere, therefore, it is possible to do not need the large-scale device of vacuum deposition apparatus etc., manufacturing cost can be reduced significantly.
In addition, in vacuum vapour deposition, formed when being mixed with the film of multiple material and use vapour deposition method altogether, but critically must control the evaporation rate of each material in the method respectively, be difficult to the uniform film of stable formation composition.To this, according to electrojet method, by means of only being dissolved in solution with making each homogenize material, the uniform film of composition can be obtained, therefore, it is possible to easily stably form blending constituent film.
In addition, organic EL element of the present invention can be used in various device, such as, the display of PC and TV is self-evident, all applicable to video camera, digital camera, navigation system, sound equipment reproducer (automobile audio, sound system etc.), game machine, portable data assistance (laptop computer, mobile phone, portable game machine or e-book etc.) etc.Can certainly be used in various lighting apparatus.
Symbol description
1 by film forming object
2 solution side electrodes
3 spray nozzles
4 high voltage sourcies
5 masking liquids
10 substrates
11a ~ 11c lower electrode
12 solution side electrodes
13 spray nozzles
14 high voltage sourcies
15 masking liquids
20 glass substrates
21 lower electrodes (anode)
22 organic layers
23a hole injection layer (second layer).
23b hole transporting layer (second layer).
24 luminescent layers
25 electron supplying layers
26 upper electrodes (negative electrode)
27 distance pieces
28 sub-pixels
30 electrical spraying device
31 dissemination apparatus
31a capillary
32
33 first high voltage sourcies
34 coated side electrodes
35 voltage-operated devices
35a second high voltage source
50 light-emitting components
51 glass substrates
52 lower electrodes (anode)
53 upper electrodes (negative electrode)
54 organic layers
56 hole injection layers
57 hole transporting layers
58 electronic barrier layers
59R luminescent layer
60G luminescent layer
61B luminescent layer
62 hole blocking layers
63 electron supplying layers
64 electron injecting layers
Claims (10)
1. a manufacture method for organic EL element, is characterized in that, comprising:
Lower electrode formation process, substrate forms lower electrode; With
Utilize the film formation process of electrojet method, the electric field being set as at least more than 100KV/m is formed between injection nozzle and the substrate being formed with described lower electrode, in this condition, the solution of coating material charged before distribution is dispersed in from described injection nozzle to described substrate
In described film formation process, control the current potential of described lower electrode,
The drop of miniaturization is made to drop to by film forming object with the state remaining solvent, make the drop landed each other to retain the state drying of granular shape, thus, be that the microparticle of below 100nm combines the gapless membrane structure patterning formed continuously by the particle diameter of granular core.
2. the manufacture method of organic EL element as claimed in claim 1, is characterized in that:
In described lower electrode formation process, form multiple described lower electrode,
Described film formation process comprises the control of Electric potentials operation of the current potential controlling described lower electrode,
In described control of Electric potentials operation, the process of giving the electric charge of the same race with the solution of described coating material is carried out at least any one lower electrode in described multiple lower electrode.
3. an organic EL element, its organic EL element manufactured for using the manufacture method described in claim 1 or 2, is characterized in that:
Possess: described substrate; Comprise the pair of electrode layers of described lower electrode and upper electrode; And organic layer,
Described organic layer is arranged between described pair of electrode layers,
Described pair of electrode layers and described organic laminate on described substrate,
Described organic layer has more than one layer, and this more than one layer comprises the luminescent layer by applying voltage and luminescence,
At least one layer that described organic layer has, uses described electrojet method to be patterned as described membrane structure.
4. organic EL element as claimed in claim 3, is characterized in that:
Described luminescent layer has described membrane structure.
5. organic EL element as claimed in claim 3, is characterized in that:
Described organic layer also comprises the second layer as at least any one the performance function in electric charge injection layer and charge transport layer,
The described second layer has described membrane structure.
6. the organic EL element according to any one of claim 3 ~ 5, is characterized in that:
Described membrane structure comprises low molecule organic material.
7. organic EL element as claimed in claim 4, is characterized in that:
Described luminescent layer comprises and has described membrane structure and the different multiple luminescent layers of the color of luminescence.
8. organic EL element as claimed in claim 5, is characterized in that:
The described second layer comprises and has described membrane structure and the different multiple second layers of thickness.
9. organic EL element as claimed in claim 5, is characterized in that:
The described second layer comprises and has described membrane structure and the different multiple second layers of material.
10. an organic EL display, is characterized in that:
It uses the organic EL element according to any one of claim 3 ~ 9 to be formed.
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| JP2009-157442 | 2009-07-02 | ||
| PCT/JP2010/003899 WO2011001613A1 (en) | 2009-07-02 | 2010-06-11 | Organic el element, process for manufacturing organic el element, and organic el display device |
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| JP5834357B2 (en) * | 2011-10-24 | 2015-12-16 | 新日鉄住金化学株式会社 | Organic electroluminescence device and method for manufacturing the same |
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| TWI276366B (en) | 2002-07-09 | 2007-03-11 | Semiconductor Energy Lab | Production apparatus and method of producing a light-emitting device by using the same apparatus |
| US20070157880A1 (en) | 2003-02-19 | 2007-07-12 | Akihiko Tanioka | Immobilizing method, immobilization apparatus, and microstructure manufacturing method |
| JP2006116491A (en) * | 2004-10-25 | 2006-05-11 | Matsushita Electric Ind Co Ltd | Electrostatic spraying type capillary and electrostatic spraying apparatus using it |
| GB0524979D0 (en) | 2005-12-07 | 2006-01-18 | Queen Mary & Westfield College | An electrospray device and a method of electrospraying |
| JP5207334B2 (en) * | 2006-02-28 | 2013-06-12 | 独立行政法人理化学研究所 | Micropattern forming apparatus, micropattern structure, and manufacturing method thereof |
| JP4656038B2 (en) * | 2006-10-16 | 2011-03-23 | パナソニック株式会社 | Electrostatic spraying method and microfluidic chip |
| US8461758B2 (en) * | 2008-12-19 | 2013-06-11 | E I Du Pont De Nemours And Company | Buffer bilayers for electronic devices |
-
2010
- 2010-06-11 WO PCT/JP2010/003899 patent/WO2011001613A1/en active Application Filing
- 2010-06-11 CN CN201080029373.1A patent/CN102484207B/en not_active Expired - Fee Related
- 2010-06-11 JP JP2011520762A patent/JP5940808B2/en not_active Expired - Fee Related
- 2010-06-11 KR KR1020127001312A patent/KR101398237B1/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1538787A (en) * | 2003-04-15 | 2004-10-20 | 精工爱普生株式会社 | Membrane forming method and forming device, electronic device and its manufactoring method, electronic machine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011001613A1 (en) | 2012-12-10 |
| CN102484207A (en) | 2012-05-30 |
| US8853678B2 (en) | 2014-10-07 |
| WO2011001613A1 (en) | 2011-01-06 |
| US20120104429A1 (en) | 2012-05-03 |
| KR101398237B1 (en) | 2014-05-23 |
| JP5940808B2 (en) | 2016-06-29 |
| KR20120024978A (en) | 2012-03-14 |
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